Interpolymers of allyl alcohol and alkyl diesters of an alpha-unsaturated dicarboxylic acid



Patented May 16, 1950 INTERPOLYMERS OF ALLYL ALCOHOL AND ALKYL DIESTERS OF AN ALPHA-UNEAT- URATED DICARBOXYLIC ACID Pliny 0. Tawney, Passalc, N. J., assignor to United States Rubber Company, New York, N. Y., a corporation oi New Jersey No Drawing. Application April 18, 1946, Serial No. 663,244

(Cl. mill-78$) 4 (llaims. i

This invention is concerned with the prepara tion of a new class of soluble, thermoplastic polymers which can undergo chemical modifications to produce soluble, unsaturated resins ca-= pable of further polymerization to a solvent and heat-resistant state. Particularly, the invention relates to soluble, fusible polymeric materials prepared by the direct copolymerization of a 2-propenyl alcohol with at least one monomeric ester of a non-enic (i. e., non-oleiinic and nonacetylenic) monohydric alcohol and an a-unsaturated dicarboxylic acid, and to the unsaturated resins obtained by alcoholysis of said copolymers with 2-propenyl alcohols.

This application is a continuation-in-part of my application Serial No, 515,431, filed December 23, 1943, now abandoned.

It is known that copolymers of a 2-propenyl alcohol and an ester of an lit-unsaturated dicarboxylic acid can be prepared by hydrolyzing a copolymer of a 2-propenyl ester and an a-unsaturated dicarboxyllc acid ester as exemplified in the following equation, involving a copolymer of allyl acetate and diethyl fumarate.

However, I have found that in practice this method is open to at least two objections. First, the hydrolysis reaction is necessarily of long duration because of the high molecular weight of the ester involved, i. e., the copolymer. Such long reaction times severely curtail the production capacity of a reaction vessel and often facilitate secondary reactions, e. g., concurrent hydrolysis of the dicarboxylic acid ester groups, which may lead to products of an undesirable and/or uncertain character. Second, because of the disposition and proximity of adjacent sidechain groups in the copolymer, it is extremely dificult to insure complete hydrolysis of the allyl ester groups and thus provide the maximum number of hydroxyl groups. The presence of free hydroxyl groups in these interpolymers is important not only because they permit further modifications by treatment with various reactive chemical agents but also to achieve products of maximum softening temperature and resistance to carbonylic and hydrocarbon solvents.

It is an object of this invention to avoid the above mentioned difiiculties and to secure uni= form products whose properties and chemical structure are easily reproducible. This object I attain by interpolymerizing directly 9. 2-propenyl alcohol selected from the class consisting of allyl alcohol and 2-alkyl-allyl alcohols, e. g., methallyl alcohol and ethallyl alcohol, with one or more esters of a-unsaturated dicarboxylic acids elected from the class consisting of maleic, iumaric, citraconic, mesaconic, and itaconic acids, and the monohydric non-enic alcohols, such as methyl, ethyl, propyl, butyl, isobutyl, amyl, cyclohexyl, benzyl, and phenethyl alcohols, and the corre= spending phenyl and tolyl diesters. The latter illustrate aromatic diesters of said acids. Particular examples of such esters, among others, are dimethyl citraconate, dibutyl maleate, dimethyl mesaconate, and di-2-ethyl-hexyl itaconate. They all are simple diesters. Groups like benzyl and phenethyl are functionally aliphatic like methyl, ethyl, etc. The esters may be described as monomeric simple diesters of a-unsaturated dibasic acids in which the ester-forming groups (replacement for carboxylic hydrogen) are aromatic radicals or non-enic functionally aliphatic radicals.

Although the 2-Dropenyl alcohols homopolymerize with difilculty, and in low yields, to products of very low molecular weight, I have found that they can be readily interpolymerized with esters of the above-mentioned iii-unsaturated dicarboxylic acids to give excellent yields of moderately high molecular weight interpolymers.

The formation of my initial copolymers is exemplified by the following equations involving methallyl alcohol and diethyl iumarate.

as indicated above, undergoes two secondary reactions with the elimination of an alcohol from the iumaric ester portion to form a new and useful class of polymeric materials.

1. The fumarlc ester unit of the polymer chain undergoes an alcohol interchange reaction with the monomeric methallyl alcohol in the reaction mixture, thus:

In ymcrired dlethyl Methailyl alcohol --v a unit ymsrizod mcthallyl Ethanol byl fumarate OH--OH-- oo o This alcoholysis reaction is favored by an excess of the 2-propenyl alcohol in the reaction mixture. 2 A fumaric ester unit of the interpolymer l ELI 0311503 Hl-O- 00 to This lactone formation is favored by high reaction temperatures.

My new interpolymers prepared from methallyl alcohol and diethyl fumarate therefore consists of a linear polymeric chain containing a plurality of the following units:

lethally] alcohol Diethyl iumarate unit unit and persuli'ates) for the emulsion polymerizations, while for the en masse and solution polymerizations organic peroxides such as acetyl peroxide, benzoyl peroxide, ter-butyl hydrogen peroxide, lauroyl peroxide and succinyl peroxide are satisfactory.

According to their intended use, the properties of my interpolymers, such as their flexibility, toughness, tensile strength, solubility, etc., can be varied over a considerable range by altering the relative proportions of the monomeric starting materials. The molar ratio of the z-propenyl alcohol to the a-unsaturated dicarboxylic acid ester in the reactant mixture is preferably maintained in the approximate range of from 10:1 to 1:5 since the copolymers obtained from reactant mixtures outside this range are often inferior with respect to yield and likewise entail considerable purification to remove unreacted monomers. Reactant mixtures containing over (by weight) of the 2-propenyl alcohol yield interpolymers which are relatively hard and tough, and contain the maximum number of hydroxyl groups, and the high concentration of 2-propenyl alcohol likewise encourages the secondary alcoholysis reaction whereby unsaturated interpolymers are obtained. When the reactant mixture contains over 50% (by weight) of the a-unsaturated dicarboxylic acid ester, the resulting interpolymers tend to be of the softer and more flexible type. For a given molar ratio of Z-propenyl alcohol to the a-unsaturated dicarboxylic ester, the flexibility and hydrocarbon-miscibility of the resulting copolymers can be increased by employing the rat-unsaturated dicarboxylic acid esters of higher alcohols, e. g., of n-butanol and hexanol.

By reacting the copolymerizable monomers in the presence of a solvent, the resulting solutions of the interpolymers can be employed directly as coating and impregnating compositions, and in the case of the emulsion polymerizations, the interpolymers are obtained as milky latices which may be used in the same manner as the above Lactone unit Methallyl ethyl iumarate unit OH; --OH-OH 0 1 OH Oil- OHg-l I 0 (ISO OH:-4l CH-OH- (BO 10 E011 OCsHs 001B; HrO- 0 430 601% 6011.0 (CH;)=OH1 Although the above remarks concerning the structure of my new polymeric products have been directed specifically to copolymers of methallyl alcohol and diethyl fumarate, they are generally applicable to all the copolymers of the 2- propenyl alcohols with esters of a-unsaturated dicarboxylic acids as previously defined, i. e., the copolymers of the 2-propenyl alcohols with the aforesaid a-unsaturated dicarboxylic esters all undergo the secondary reactions of alcoholysis and lactonization.

For the preparation of my new interpolymers, I may carry out the polymerization reaction en masse, i. e., in a mixture of monomeric materials only, or if desired, in the presence of solvents, diluents, emulsifying agents, etc. The reaction temperatures may range from about 25 C. up to the reflux temperature of the reaction mixture and for overall economy it is preferable to operate in the upper part of this range.

To accelerate the lnterpolymerizations, there may be used inorganic peroxides such as hydrogen peroxide and per-salts (e. g., percarbonates mentioned solutions. If rubber-like products are desired, plasticizers or softening agents can be conveniently incorporated with the interpolymers by adding them to the solutions or emulsions of the interpolymers prior to isolating the products. The interpolymers are obtained from solution by precipitating them with a nonsolvent such as n-hexane or from the emulsion by fiocculating with electrolytes. The products are purified by extracting any unreacted starting materials with solvents in which the interpolymers are insoluble, and drying. They are then readily applicable to the preparation of filaments, sheets and castings whose resistance to attack by hydrocarbon solvents is proportional to the amount of free hydroxyl groups present in the interpolymer.

My products are usually transparent and hence are suitable for the incorporation of dyes and pigments. To avoid contamination and discoloration, the interpolymerizations may be carried out in glass-lined vessels and under a blanket of inert gas.

My copolymers are not only suitable for many of the applications of thermoplastic resins, but they are of further potential utility by virtue of their chemical structure. For example, the pres- The alooholysis reaction is particularly well adapted to the production of interpolymers of a 2-propenyl alcohol with an ester of an a-unsaturated dicarboxylic acid and an alcohol which has ence of free hydroxyl groups permits of considera normal boiling point lower than that of the able modification in the properties of the copolymers by treatment with chemical hydroxylreactive agents known to react with primary hydroxyl groups, such as organic acids or their 2-propenyl alcohol (e. g., diethyl iumarate, diisopropyl itaconate, etc.). The interchange can be accelerated by regulating the temperature so that the lower boiling of the alcohols, freed duranhydrides or halides, and isocyanates, aldehydes, Z110 ing the interchange reaction, e. g., methanol or etc. Moreover, by employing poly'functional reagents such as dibasic acids or their anhydrides, diisocyanates, etc., my copolymers can be easily cross linked and thereby rendered impervious to ethanol, can be removed by continuous or intermittent distillation from the reaction mixture. At the end of the reaction, the unreacted 2- propenyl alcohol can be removed by distillation attack by solvents. Alternatively, my intcrpoly- 1-5 or extraction, and if necessary the residue can mers can be cross-linked by treatment with unsaturated acids or alcohols or their derivatives, reactive with hydroxyl groups, such as methacrylic acid, allyl alcohol, acrylyl chloride, methallyl be further purified by dissolving'it in a solvent such as acetone, and precipitating it with a nonsolvent such as n-hexane.

The pure alcoholyzed product is a clear, therchloride, etc., followed by polymerization or comopiastic material soluble in many solvents. At

polymerization of the unsaturated polymeric esters so produced to insoluble, infusible resins.

A further advantage of my copolymers isthat they are easily soluble in certain solvents, particelevated temperatures such as 180 0.. and/or in the presence of polymerization catalysts such as organic peroxides, it is capable of being converted to a transparent, insoluble, infusi'ble resin.

ularly z-propenyl alcohols. Thus thecopolymers The convertible resin is suitable for use in coatof methallyl alcohol and diethyl fumarate dissolve readily in methallyl alcohol to form clear solutions of high concentration. The high solubility of my interpolymers in 2propeny1 alcohols ing, impregnating and laminating operations where pre-formed articles capable of being "set or cured are desired. Compatible plasticizers, softening agents, pigments, fillers, etc., can be is particularly advantageous since it permits an so readily incorporated with the resin in the soluble,

alcohol interchange to be carried out between my linear interpolymer esters and 2-propenyl alcohols without the need of a mutual solvent such as is required for practical purposes in the alcoholysis of many homopolymers, thereby effecting .35

a savin both in time and. material cost. The alcoholysis of my interpolymers with 2-propenyl alcohols leads to a new class of soluble, unsaturated resins of wide utility since they can be thermoplastic stage prior to final cure.

The unsaturated interpolymer can also be ccpolymerized with a wide variety oi polymerizable ethylenic monomers, such as methyl acrylate, methyl methacrylate, diallyl fumarate, and ally] acrylate. Furthermore, my alcoholyzed interpolymers are readily converted to insoluble, infusible materials "40 miscible over a wide range of proportions with by further polymerization.

As mentioned, the formation of my interpolymers is attended by a secondary reaction of alcoholysis. This effect can be employed advanmany of the mentioned copolymerizable compounds, and the solutions containing high concentrations of the alcoholyzed interpolymer-s in the appropriate monomers often have suflicienttageously, for, Since my interpolymers are highly 1y low viscosities to permit their application by soluble in Z-propenyl alcohols, the copolymerization and alcoholysis reactions can be carried out concurrently without the necessity of isolating the initial interpolymer.

When large amounts of unsaturation are to be so introduced, however, it is preferable to first isolate and purify the copolymer and then to carry out the alcoholysis in a subsequent reaction. This method is particularly advantageous when it is desired to alcoholyze my interpolymers with 2.15

or chlorallyl alcohol and heating the resulting 59 solution. Catalysts of the basic type, such as sodium hydroxide, or of the acidic type, such as p-toluene sulphonic acid, may be added to accelerate the alcohol interchange. When the alcoholysis involves 2-alkylallyl alcohols, e. g.,

methallyl alcohol, a basic catalyst is preferred since the 2-aikylallyl alcohols tend to rearrange to aldehydes in the presence of acids.

The amount of unsaturation introduced into spraying, brushing, or dipping. Elevated temperatures, e. g., 15(l C., and/or a polymerization catalyst, such as an organic peroxide, readily convert these thermosetting compositions to insoluble, infusible products with a minimum of the cracking, blowing and shrinking often associated with the elimination of a volatile, nonpolymerizable solvent from the cured product.

My interpolymers which have been alcoholyzed to such an extent that the percentage of 2-propenyl alcohol radicals therein is substantially greater than that of the saturated alcohol radicals, are particularly advantageous for this purpose because of their high rate of solution in the copolymerizable monomers and because, of the speed of the resulting conversion to insoluble, infusible products.

The following examples disclose the practice of my invention in more detail, all parts being by weight:

Example 1 (a) A mixture of 174 parts oi allyl alcohol, 516 parts of diethyl fumarate, and 10.35 parts of benzoyl peroxide is heated for 21 hours at gentle the interpolymer can of course be varied by al-"lo reflux. The reaction mixture is then cooled and terin the time of reaction for the alcohol interchange. Where long reaction times are involved, inhibitors such as copper, hydroquinone, etc., may

-be added to the reaction mixture to avert premapoured into a commercial grade of n-hexane. The precipitated copolymer is further purified by repeated solution in acetone and precipitation with n-hexane. After drying to constant weight ture polymerization of the aicoholyzed product. 7 in vacuo parts of polymeric solid are obtained Weight, Interpolymeric Unit Per Moles Cent Allyl Al h l 0. l. 0 Diethyl Fumarate 30. 00 20. 25 Lacton 59. 72 37.00 Allyl Ethyl Fumarate 9. 78 6. 17

This corresponds to an interpolymer derived from approximately 81% of diethyl fumarate and 19% of allyl alcohol.

(b) A mixture of 50 parts of the interpolymer. 17.2 parts of n-butyl acid maleate, and 0.067 part of p-toluene sulfonic acid is heated with agitation under a blanket of carbon dioxide for 2.5 hours at 170-180 C. Seven parts of the viscous reaction product are mixed with 3.0 parts of vinyl acetate and 0.1 part of benzoyl peroxide and heated in a cylindrical mold for 2 hours at 40 C., then for 1 hour at 60 C., and finally for 1.8 hours at 110 C. The resulting clear, somewhat flexible casting is insoluble in acetone. A similar casting is obtained when methyl acrylate is copolymerized with the resin in place of the vinyl acetate above.

Example 2 (a) A copolymer of allyl alcohol and dimethyl itaconate is prepared by heating a mixture of 237 parts of dimethyl itaconate, 87 parts of allyl alcohol, and 4.86 parts of benzoyl peroxide, at 85-90 C., for 17.5 hours. After isolation and purification, as in Example 1 above, 185 parts of a white polymeric solid are obtained which dissolve readily in acetone, cyclohexanone, acetonitrile. and in 2-propenyl alcohols.

Analysis: FoundC, 56.44%; H, 7.10%; iodine number 4.1

The analysis indicates the following compositlon:

Interpolymeric Unit Ygfi g Moles Allyl Alcohol 28. O 1. 0 Dimethyl Itaconate 61. 3 0. 808 Allyl Methyl Itaconate 2. 93 0. 033 Tlaotnm 7. 77 Q. 087

This corresponds to an interpolymer derived from approximately 69.5% of dimethyl itaconate and 30.5% of allyl alcohol.

(1)) A mixture of 32.4 parts of the interpolymer and 7.0 parts of maleic anhydride, is heated at 105-110 C. for 8 minutes. The reaction is halted by quickly cooling to room temperature.

Three parts of the reacted mixture, together with 2 parts of triethylene glycol, are dissolved in a mixture of 1 part of cyclohexanone and 10 parts of acetone. The solution is poured on a glass panel, and after the solvent has evaporated. the

8 resulting film is baked at 180 C. for 0.5 hour, forming a hard, clear, insoluble coating which displays good scratch resistance.

Example 3 A mixture of 32.1 parts of allyl alcohol, 01.0 parts of dimethyl itaconate, and 1.79 parts of benzoyl peroxide is dissolved in 29 parts oi cyclohexane and heated for 9.7 hours at 87-89 C. The product is purified by dissolving it in acetone and precipitating it with n-hexane. The vacuumdried copolymer is a white solid which is soluble in acetone, allyl alcohol, and methallyl alcohol, but insoluble in n-hexane and in benzene.

Analysis: Found-C, 55.86%; H, 6.82%; iodine number (Wijs) 4.7 [1 10, 0.0243.

The analysis indicates that the polymer contains approximately 66.8% by weight of interpolymerized dimethyl itaconate units, 9.9% of allyl alcohol units, 3.34% of allyl methyl itaconate units, and 20.0% of the isomeric lactone units. This corresponds to a copolymer prepared from approximately 16.3% by weight of allyl alcohol and 83.7% of dimethyl itaconate.

A solution of 3 parts of the interpolymer dissolved in a mixture of 5 parts of acetone and 1 part of cyclohexanone is flowed onto a glass panel and baked at 200 C. for 20 minutes to yield a clear, adherent film.

Example 4 A mixture of 15.82 parts of dimethyl ltaconate. 7.20parts of methallyl alcohol, and 0.241 part of benzoyl peroxide is heated under an atmosphere of nitrogen for 70 hours at 60 C. The product is purified by repeatedly dissolving it in acetone and precipitating it with n-hexane and after being dried in vacuo, it amounts to 7.49 parts of polymeric solid which is readily soluble in ketones, and 2-propenyl alcohols. It softens at C. and becomes fluid at C.

Analysis: Found-C, 55.66%; H, 6.94%.

From the analysis the interpolymer is calculated to contain approximately 81.5% by weight of dimethyl itaconate units, 9.5% of methallyl alcohol units and 9.0% of methallyl methyl itaconate and/or the isomeric lactone units. This corresponds to an interpolymer formed from approximately 87.8% by weight of dimethyl itaconate and 12.2% of methallyl alcohol.

Five parts of the interpolymer are intimately mixed with 1.0 part of maleic anhydride and heated to C. The solution gels to an insoluble mass within 15 minutes.

Example 5 A mixture of 68.0 parts of allyl alcohol, 201.8 parts of diethyl fumarate and 5.6 parts of benzoyl peroxide is dissolved in 68.0 parts of cyclohexane, and the resulting solution is heated at 87-90 C. for 13.75 hours. After the usual purification, 41.5 parts of a clear, plastic solid are obtained which is soluble in acetone and allyl alcohol but insoluble in n-hexane.

Analysis: Found-C, 57.95%; H, 7.08%; iodine number 7.0 [1 10 0.066.

The analysis indicates an interpolymer containing approximately 26.4% by weight of diethyl fumarate units, 0.8% of allyl alcohol units, 6.97% of allyl ethyl fumarate units, and 65.8% of the isomeric lactone units.

Thus the interpolymer is formed from approximately 80% by weight of diethyl fumarate and 20% of allyl alcohol.

asomu Example 6 (a) This illustrates the alcoholysis of my new interpolymers with 2- propeny1 alcohols. Sixty parts of a copolymer prepared as in Example 2(a) are dissolved in 250 parts of methallyl alcohol and refluxed for 14 hours in the presence of 0.2 part of sodium hydroxide as an esterification catalyst. During the alcohoiysis a mixture of methallyl and methyl alcohol is removed by distillation. At the conclusion of the reaction, the reaction mixture is decanted from the catalyst and unreacted methallyl alcohol is removed by distillation under diminished pressure. The residue is purified by dissolving it in acetone and precipitating with n-hexane, and after drying to constant weight, 50 parts of a white solid are obtained which softens at approximately 60 C. and is readily soluble in acetone and in 2-propenyl alcohols, such as allyl and methallyl alcohols.

Analysis: FoundIodine number, 12.0.

The increase in the iodine number over that of the original interpolymer indicates that -unsaturation has been introduced into the polymer by alcoholysis with methallyl alcohol.

(1)) Six parts of the alcoholyzed interpolymer prepared in (a) above are dissolved in 4 parts of methyl acrylate with 0.10 part of benzoyl peroxide, and the resulting solution is heated for 5 hours at 60 C. and then for 2 additional hours at 110 C. The resulting casting is hard, tough and insoluble in acetone.

A similar but harder product is obtained when allyl acrylate is substituted for the methyl acrylatein (b) While I have shown and described various embodiments of the invention, it is to be understood that the invention is susceptible to those modiflcations which appear within the spirit of the invention and the scope of the appended claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A method which comprises copolymerizing directly, in the presence of a peroxidic polymerization catalyst, a monomeric 2-alkenyl alcohol selected from the class consisting of allyl alcohol, methallyl alcohol and ethallyl alcohol, and a monomeric souble diester of an alpha-unsaturated dicarboxylic acid with a monohydric alkanol, at

a temperature from about 25 C. up to the reflux 2,280,242

temperature at atmospheric pressure of the reaction mix to form a soluble copolymer of said 10 monomers, and in which the molar ratio oi the alcohol to the diester in the original reaction mix ranges from 10: 1 to 1:5.

2. A method which comprises copolymerizing directly, in the presence of a peroxidic polymerization catalyst, a monomeric 2-alkenyl alcohol selected from the class consisting of allyl alcohol, methallyl alcohol and ethallyl alcohol, and a monomeric soluble diester of an alpha-unsaturated dicarboxylic acid with a monohydric alkanol, at a temperature from about 25 C. up to the reflux temperature at atmospheric pressure of the reaction mix to form a soluble copolymer of said monomers, and concurrently alcoholyzing the soluble copolymer, whereby to form an unsaturated alcoholyzed soluble interpolymer, and in which the molar ratio of the alcohol to the diester ilnsthe original reaction mix ranges from 10:1 to

A method which comprises heating directly ,with each other, in the presence or a peroxidic molar ratio of the alcohol to the diester in the original reaction mix ranges from 10:1 to 1:5.

4. A soluble unsaturated alcoholyzed interpolymerizate of a monomeric 2-alkenyl alcohol selected from the class consisting of allyl alcohol, methallyl alcohol and ethallyl alcohol, and a monomeric soluble diester of an alpha-unsaturated dicarboxylic acid with a monohydric alkanol, produced as set forth in claim 2.

PLINY O. TAWNEY.

REFERENCES CITED The following references are of record file of thispatent:

UNITED STATES PATENTS in the Number Name Date 2,221,663 Rothrock Nov. 12, 1940 Kropa et a1. Apr. 21, 1942 2,332,900 DAlelio Oct. 26, 1943 Certificate of Correction Patent No. 2,507,871 May 16, 1950 PLINY O. TAWNEY It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 3, lines 28 to 32, inclusive, for that portion of the formula reading am-E rea am-E L d L and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 1st day of August, A. D. 1950.

THOMAS F. MURPHY,

Assistant Uomme'ssz'oner of Patents. 

1. A METHOD WHICH COMPRISES COPOLYMERIZING DIRECTLY, IN THE PRESENCE OF A PEROXIDIC POLYMERIZATION CATALYST, A MONOMERIC 2-ALKENYL ALCOHOL SELECTED FROM THE CLASS CONSISTING OF ALLYL ALCOHOL, METHALLYL ALCOHOL AND ETHALLYL ALCOHOL, AND A MONOMERIC SOUBLE DIESTER OF AN ALPHA-UNSATURATED DICARBOXYLIC ACID WITH A MONOHYDRIC ALKANOL, AT A TEMPERATURE FROM ABOUT 25*C. UP TO THE REFLUX TEMPERATURE AT ATMOSPHERIC PRESSURE OF THE REACTION MIX TO FORM A SOLUBLE COPOLYMER OF SAID MONOMERS, AND IN WHICH THE MOLAR RATIO OF THE ALCOHOL TO THE DIESTER IN THE ORIGINAL REACTION MIX RANGES FROM 10:1 TO 1:5. 